CN101935442A - A kind of rosin polyether ester elastomer and preparation method thereof - Google Patents

Abstract

The invention provides a kind of rosin polyether ester elastomer, comprising: modified rosin, glycol and crosslinking agent; Described modified rosin is the compound shown in formula I: Described glycol is polyethylene glycol, Polytetrahydrofuran diol or polycaprolactone diol; The molar ratio of described modified rosin, glycol and crosslinking agent is 1: 1～1.5: 0.5～1; The degradability of described rosin polyether ester elastomer is 12% to 45%. The present invention uses rosin with three-membered ring phenanthrene structure as raw material, and this three-membered ring phenanthrene structure is actually a steroidal structure with strong rigidity comparable to benzene ring, so rosin is used as raw material, and After the rosin is modified, it reacts with dihydric alcohol and crosslinking agent to prepare network rosin polyether ester elastomer, which is non-toxic, degradable, and the raw material can be regenerated, and has performance similar to that of aromatic polyether ester elastomer. The invention also provides a preparation method of the rosin polyether ester elastomer.

Description

A kind of rosin polyether ester elastomer and preparation method thereof

technical field

The invention relates to the field of polymer synthetic material preparation, in particular to a rosin polyether ester elastomer and a preparation method thereof.

Background technique

Rosin is extracted from the secretions of pine trees. It is a rich natural resource and a renewable, non-toxic, degradable and low-cost resin material. It is often used as welding adhesives or coatings, Thickener or emulsifier in binder. The main component in rosin is abietic acid. The typical structural formula of described abietic acid is the compound shown in II, III, IV, V,

When heated above 100°C, the abietic acids shown in formulas II, III, and IV are isomerized to form abietic acids shown in formula V, and the abietic acids shown in formula V are L-pimaric acid, which can be combined with other Compounds with conjugated double bonds undergo Diels-Alder addition reactions.

Polyether ester elastomer is an elastomer obtained by copolymerization of polyhydroxyl compounds and polycarboxylate compounds. Due to its excellent toughness, fatigue resistance, wear resistance and corrosion resistance, it is widely used in automobiles, aerospace, petrochemical, biological technology and other fields. With the development of science and technology, degradable polyether ester elastomers have become the focus of people's research, especially the research on network polyether ester elastomers is the most in-depth, because network polyether ester elastomers have a wide range of performance adjustment, and It is environmentally friendly and degradable.

The polyether ester elastomers in the prior art all use by-products of petroleum refining. With the increasing depletion of petroleum resources, the price of raw materials used to prepare aromatic polyether ester elastomers and aliphatic polyether ester elastomers Also getting higher and higher.

Contents of the invention

The technical problem to be solved by the present invention is to provide a rosin polyether ester elastomer, which is non-toxic, degradable, has renewable raw materials and low production cost.

In order to solve the above problems, the invention provides a kind of rosin polyether ester elastomer, comprising modified rosin, dihydric alcohol and crosslinking agent; Described modified rosin is the compound shown in formula I:

Wherein, n=3～15; The dibasic alcohol is polyethylene glycol, polytetrahydrofuran diol or polycaprolactone diol; The molar ratio of the modified rosin, dibasic alcohol and crosslinking agent is 1:1 ~1.5:0.5~1; the degradability of the rosin polyether ester elastomer is 12%~45%.

Preferably, the crosslinking agent is citric acid or glycerin.

The present invention also provides a kind of preparation method of rosin polyether ester elastomer, comprising:

A) prepare the modified rosin shown in formula I;

b) Mix modified rosin, glycol, and crosslinking agent in a molar ratio of 1:1 to 1.5:0.5 to 1 to obtain a mixture; the glycol is polyethylene glycol, polytetrahydrofuran glycol or polyethylene glycol Lactone diol; The modified rosin is a compound shown in formula I;

c) heating the mixture, the modified rosin and the dibasic alcohol undergo ester condensation and are crosslinked by a crosslinking agent to obtain a rosin polyether ester elastomer; the degradability of the rosin polyether ester elastomer is 12 %~45%.

Preferably, the crosslinking agent is citric acid or glycerin.

Preferably, a first catalyst is added into the mixture, and the first catalyst accounts for 0.5%-1% by weight of the modified rosin.

Preferably, the first catalyst is zinc oxide, stannous oxalate or tetrabutyl titanate.

Preferably, step a) is specifically:

a1) Mix rosin and polyether acrylate in a molar ratio of 1:0.5, add a second catalyst accounting for 0.5-1% of the mass of rosin to obtain a mixture; the structural formula of the polyether acrylate is:

Wherein n=3～15.

a2) heating the mixture obtained in step a1), a Diels-Alder addition reaction occurs to obtain an addition product;

a3) mixing the addition product with petroleum ether to separate out the modified rosin.

Preferably, the second catalyst is p-toluenesulfonic acid, hydroquinone or catechol.

Preferably, the rosin is one or more of the abietic acids shown in formula II, III, IV or V:

Preferably, the heating temperature in step a2) is 170°C-220°C.

The present invention uses rosin with three-membered ring phenanthrene frame structure as raw material, and this three-membered ring phenanthrene frame structure is actually a steroidal structure, rigidity can be similar to benzene ring, so use rosin as raw material, and described After rosin is modified, it reacts with diol and crosslinking agent to prepare network rosin polyether ester elastomer, which is non-toxic, degradable, and the raw material is renewable, and has similar properties to aromatic polyether ester elastomer. Rosin polyether ester elastomer is essentially a kind of polyether ester elastomer, and the degradability of rosin polyether ester elastomer provided by the present invention can reach 12% to 45% through experiments, and rosin belongs to renewable natural resin , non-toxic and harmless, low cost, suitable for industrial production, solves the problem of using non-renewable resources as raw materials for polyether ester elastomers in the prior art, and reduces production costs.

The present invention also provides a preparation method of rosin polyether ester elastomer, a) preparing modified rosin; b) preparing modified rosin, glycol, and crosslinking agent in a molar ratio of 1:1～1.5:0.5～ 1 mixed to obtain a mixture; the dibasic alcohol is polyethylene glycol, polytetrahydrofuran diol or polycaprolactone diol; the modified rosin is a compound shown in formula I; c) heating the mixture, the obtained The modified rosin and the glycol undergo ester condensation and are cross-linked by a cross-linking agent to obtain a rosin polyether ester elastomer. The process is simple and the reaction is controllable.

Description of drawings

The infrared spectrogram of the polyether acrylate modified rosin provided by Fig. 1 the present invention;

The infrared spectrogram of the rosin polyether ester elastomer prepared by the polyether acrylate modified rosin provided by the present invention in Fig. 2;

The scanning electron microscope observation result figure of the rosin polyether ester elastomer that Fig. 3 the present invention provides;

The scanning electron microscope observation result figure of the rosin polyether ester elastomer that Fig. 4 the present invention provides;

Fig. 5 is a diagram of scanning electron microscope observation results of the rosin polyether ester elastomer provided by the present invention.

Detailed ways

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with the examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention rather than limiting the patent requirements of the present invention.

The present invention provides a kind of rosin polyether ester elastomer, comprises modified rosin, glycol and linking agent; Described modified rosin is the compound shown in formula I:

Wherein, n=3～15; The dibasic alcohol is polyethylene glycol, polytetrahydrofuran diol or polycaprolactone diol; The molar ratio of the modified rosin, dibasic alcohol and crosslinking agent is 1:1 ~1.5:0.5~1; the degradability of the rosin polyether ester elastomer is 12%~45%.

The rosin polyether ester elastomer provided by the invention belongs to the category of polyether ester elastomers. Modified rosin is obtained by the Diels-Alder addition reaction of L-pimaric acid and polyether acrylate, so the modified rosin molecule has 2 carboxyl groups, which can be obtained by reacting with diols and citric acid or glycerin molecules network structure.

的重复单元，其中R₁可以为式1～式7所示的取代基。当R₁为式1或式4所示的取代基时，R₂、R₃可以为式1或式4所示的取代基，R₄为式4或式7所示的取代基；当R₁为式2或式5所示的取代基时，R₂、R₃可以为式2或式5所示的取代基，R₄为式5或式7所示的取代基；当R₁为式3或式6所示的取代基时，R₂、R₃可以为式3、式6所示的取代基，R₄为式6或式7所示的取代基；甘油的结构式为

所以由甘油作为交联剂的松香聚醚酯弹性体具有结构式为

的重复单元，其中R₁可以为式1～式7所示的取代基。当R₁为式1或式4所示的取代基时，R₂、R₃可以为式1、式4或式7所示的取代基；当R₁为式2或式5所示的取代基时，R₂、R₃可以为式2、式5或式7所示的取代基；当R₁为式3或式6所示的取代基时，R₂、R₃可以为式3、式6或式7所示的取代基；The structural formula of citric acid is Therefore, the rosin polyether ester elastomer with citric acid as a crosslinking agent has a structural formula of

Repeating unit, wherein R ₁ can be a substituent shown in formula 1 to formula 7. When R ₁ is a substituent shown in formula 1 or formula 4, R ₂ and R ₃ may be a substituent shown in formula 1 or formula 4, and R ₄ is a substituent shown in formula 4 or formula 7; when R When ₁ is a substituent shown in formula 2 or formula 5, R ₂ and R ₃ may be a substituent shown in formula 2 or formula 5, and R ₄ is a substituent shown in formula 5 or formula 7; when R ₁ is When the substituent shown in formula 3 or formula 6, R ₂ , R ₃ can be the substituent shown in formula 3, formula 6, R ₄ is the substituent shown in formula 6 or formula 7; The structural formula of glycerin is

Therefore, the rosin polyether ester elastomer with glycerin as the crosslinking agent has a structural formula of

Repeating unit, wherein R ₁ can be a substituent shown in formula 1 to formula 7. When R ₁ is a substituent shown in formula 1 or formula 4, R ₂ and R ₃ can be a substituent shown in formula 1, formula 4 or formula 7; when R ₁ is a substituent shown in formula 2 or formula 5 When R ₂ , R ₃ can be the substituent shown in formula 2, formula 5 or formula 7; when R ₁ is the substituent shown in formula 3 or formula 6, R ₂ , R ₃ can be the substituent shown in formula 3, Substituents shown in formula 6 or formula 7;

It should be noted that the substituents shown in the above formulas 1 to 7 all have 2 to 3 substitution positions. When one substitution position is connected to the crosslinking agent molecule, the remaining 1 substitution position can be connected to other modified rosin Compounds obtained by reacting with diols can also be linked with other crosslinker molecules. The value of k increases with the increase of the molecular weight of polytetrahydrofuran diol, and the value of p increases with the increase of the molecular weight of polycaprolactone diol.

The present invention also provides a preparation method of rosin polyether ester elastomer, comprising: a) preparing modified rosin;

b) Mix modified rosin, glycol, and crosslinking agent in a molar ratio of 1:1 to 1.5:0.5 to 1 to obtain a mixture; the glycol is polyethylene glycol, polytetrahydrofuran glycol or polyethylene glycol Lactone diol; The modified rosin is a compound shown in formula I;

c) heating the mixture, the modified rosin and the glycol undergo ester condensation and are crosslinked by a crosslinking agent to obtain a rosin polyether ester elastomer.

According to the present invention, the modified rosin is prepared by Diels-Alder addition reaction of rosin and polyether acrylate. The main components of the rosin used in the present invention are rosin acids of 4 different structures, i.e. the abietic acids of different structures shown in formula II～formula IV:

Wherein the abietic acid shown in formula II, III, IV can not react with polyether acrylate, only the abietic acid L-pimaric acid shown in formula V can react with polyether acrylate, but formula II, III, IV can react with polyether acrylate The abietic acid shown above will undergo isomerization when heated above 100°C to generate L-pimaric acid, which can react with polyether acrylate.

According to the present invention, it is preferred to heat the rosin to 170°C to 190°C under the protection of protective gas, and while stirring, mix the rosin, the polyether acrylate with the rosin molar ratio of 1:0.5, and the rosin with a mass ratio of 0.005~ 0.01:1 of the second catalyst is mixed, the stirring time is preferably 0.5h~1h, and then the temperature is raised to 200°C~220°C, and the stirring is continued for 7h~9h, the reaction stops, and the addition product is obtained, and the addition product is mixed with 30ml~ Mix and dissolve 50ml of toluene, then add the toluene solution of the addition product into 50ml~80ml of petroleum ether, and precipitate a pale yellow solid, namely modified rosin. The second catalyst may be one or more of p-toluenesulfonic acid, hydroquinone or catechol. The protective gas is N ₂ . The structural formula of the modified rosin is:

Wherein n=3～15. The number average molecular weight is 258-700.

After the preparation of the modified rosin is completed, the modified rosin is mixed with the glycol, the crosslinking agent, and preferably the added first catalyst in a molar ratio of 1:1～1.5:0.5～1 to obtain a mixture, and the mixture is heated to 200 ℃～220℃ and stir for 1h～3h, raise the temperature to 230℃～250℃ and stir for 1h～3h, then raise the temperature to 260℃～280℃ and react for 1h～2h, then finish the reaction, cool the reaction product and dry it to obtain rosin polyether Ester elastomers. According to the present invention, the dibasic alcohol is polyethylene glycol, polytetrahydrofuran diol or polycaprolactone diol. According to the present invention, the dibasic alcohol is preferably polyethylene glycol with a number average molecular weight of 200 to 2000 Or polycaprolactone with a number average molecular weight of 530-1250 or polytetrahydrofuran diol with a number average molecular weight of 230-1250. The first catalyst may be zinc oxide, stannous oxalate or tetrabutyl titanate. The crosslinking agent can be citric acid, glycerin. The reaction is preferably performed under _N2 .

The scheme of the present invention will be described in detail below with specific examples, wherein rosin is purchased from Alfa Aesar company; Polyether acrylate, polyethylene glycol, polycaprolactone, polytetrahydrofuran, citric acid, glycerol are all purchased from Aldrich company .

Example 1

Take 30g of rosin and put it in a 250ml three-necked flask, heat it to 170°C under the protection of _N2 , start the mechanical stirring, turn on the reflux condenser, put in 10.8g of polyether acrylate with a number average molecular weight of 258 and 0.15g of hydroquinone , reacted for 1.5 hours, then raised the temperature to 200°C and reacted for 7 hours. Cool down to room temperature, add 30ml of toluene to dissolve the product, add 50ml of petroleum ether for precipitation, wash with water, recrystallize the product, filter, and vacuum dry to obtain polyether acrylate modified rosin.

Example 2

Take 30g of rosin and put it in a 250ml three-necked flask, heat it to 180°C under the protection of _N2 , start the mechanical stirring, turn on the reflux condenser, put in 24.5g of polyether acrylate with a number average molecular weight of 575 and 0.20g of catechol , reacted for 1 hour, and then raised the temperature to 210° C. for 8 hours. Cool down to room temperature, add 40ml of toluene to dissolve the product, add 70ml of petroleum ether for precipitation, wash with water, recrystallize the product, filter, and vacuum dry to obtain polyether acrylate modified rosin.

Example 3

Take 30g of rosin and place it in a 250ml three-necked flask, heat it to 190°C under the protection of _N2 , start the mechanical stirring, turn on the reflux condenser, put in 29.55g of polyether acrylate with a number average molecular weight of 700 and 0.30g of p-methylbenzene Sulfonic acid, reacted for 0.5 hours, then raised the temperature to 220°C and reacted for 9 hours. Cool down to room temperature, add 50ml of toluene to dissolve the product, add 80ml of petroleum ether for precipitation, wash with water, recrystallize the product, filter, and vacuum dry to obtain polyether acrylate modified rosin.

Example 4

Get 5.0g of the polyether acrylate modified rosin prepared in Example 1, 1.16g of polyethylene glycol with a number average molecular weight of 200 and 0.55g of citric acid are placed in a 100ml three-necked flask, while adding 0.025g of zinc oxide as a catalyst, the temperature rises To 200°C, start mechanical stirring, react for 3 hours, raise the temperature to 230°C, react for 3 hours, then raise the temperature to 260°C for 2 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 5

Get 5.0g of the polyether acrylate modified rosin prepared in Example 3, 3.48g of polyethylene glycol with a number average molecular weight of 600 and 0.55g of citric acid are placed in a 100ml three-necked flask, while adding 0.025g of zinc oxide as a catalyst, the temperature rises To 200°C, start mechanical stirring, react for 3 hours, raise the temperature to 230°C, react for 3 hours, then raise the temperature to 270°C for 2 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 6

Get 5.0g of the polyether acrylate modified rosin prepared in Example 2, 12.72g of polyethylene glycol with a number average molecular weight of 2000 and 0.60g of citric acid are placed in a 100ml three-necked flask, while adding 0.03g of zinc oxide as a catalyst, the temperature rises To 210°C, start mechanical stirring, react for 2 hours, raise the temperature to 240°C, react for 2 hours, then raise the temperature to 270°C for 1.5 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 7

Get the polyether acrylate modified rosin prepared by 5.0g embodiment 1, 4.5g number average molecular weight is 530 polycaprolactone and 1.11g citric acid are placed in the 100ml there-necked flask, add 0.05g stannous oxalate simultaneously as catalyst, Raise the temperature to 190°C, start mechanical stirring, react for 2 hours, raise the temperature to 230°C, react for 3 hours, then raise the temperature to 280°C for 2 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 8

Get 5.0g of the polyether acrylate modified rosin prepared in Example 2, 4.69g of polycaprolactone and 0.18g of glycerin with a number-average molecular weight of 800 are placed in a 100ml three-necked flask, and 0.025g of stannous oxalate is added as a catalyst at the same time, and the temperature rises To 210°C, start mechanical stirring, react for 2 hours, raise the temperature to 230°C, react for 2 hours, then raise the temperature to 270°C for 2.5 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 9

Get 5.0g of the polyether acrylate modified rosin prepared in Example 3, 4.79g of polycaprolactone and 0.18g of glycerin with a number average molecular weight of 1250 are placed in a 100ml three-necked flask, and 0.025g of stannous oxalate is added as a catalyst at the same time, and the temperature rises To 200°C, start mechanical stirring, react for 2 hours, raise the temperature to 230°C, react for 2 hours, then raise the temperature to 260°C for 3 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 10

Take 5.0 g of the polyether acrylate modified rosin prepared in Example 2, 1.45 g of polytetrahydrofuran with a number average molecular weight of 230 and 0.25 g of glycerin in a 100 ml three-necked flask, add 0.03 g of tetrabutyl titanate as a catalyst, and heat up To 200°C, start mechanical stirring, react for 3 hours, raise the temperature to 230°C, react for 3 hours, then raise the temperature to 260°C for 2 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 11

Take 5.0 g of the polyether acrylate modified rosin prepared in Example 1, 4.35 g of polytetrahydrofuran with a number average molecular weight of 600 and 0.25 g of glycerol in a 100 ml three-necked flask, and simultaneously add 0.03 g of tetrabutyl titanate as a catalyst, and heat up To 200°C, start mechanical stirring, react for 2.5 hours, raise the temperature to 230°C, react for 2.5 hours, then raise the temperature to 260°C for 1.5 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

Example 12

Take 5.0 g of the polyether acrylate modified rosin prepared in Example 3, 7.18 g of polytetrahydrofuran with a number average molecular weight of 1250 and 0.35 g of glycerin in a 100 ml three-necked flask, add 0.05 g of tetrabutyl titanate as a catalyst, and heat up To 200°C, start mechanical stirring, react for 3 hours, raise the temperature to 230°C, react for 3 hours, then raise the temperature to 260°C for 2 hours. The product was cooled to room temperature, rinsed with absolute ethanol, filtered, and vacuum-dried to obtain a cross-linked elastomer.

The rosin polyether ester elastomers prepared in Examples 4 to 12 were detected, and the thermal decomposition temperature was detected by a thermogravimetric analyzer Q500 (TA, USA). The detection environment was N ₂ , the heating rate was 10°C/min, and the temperature Range: 50-500°C; the elongation at break and tensile modulus were tested on an Instron-5869 testing machine with a tensile rate of 500mm/min; the glass transition temperature was tested using a differential scanning calorimeter Mettler Toledo DSC 822e, and the temperature was raised Rate 10°C/min, temperature range: -80～50°C; Degradability: It is the weight loss of the sample after 7 days in an alkaline solution with a concentration of 0.01mol/L at 25°C.

Table 1 Elastomer performance table

The rosin polyether ester elastomer provided by the present invention and its preparation method have been described in detail above. The principles and implementation methods of the present invention have been explained by using specific examples in this paper. The description of the above examples is only used to help understand the present invention. The method of the invention and its core idea, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made to the present invention, and these improvements and modifications also fall within the scope of this invention. within the protection scope of the invention claims.

Claims (9)

1. a rosin polyether ester elastomer, is characterized in that, comprises modified rosin, glycol and linking agent; Described modified rosin is the compound shown in formula I:

Wherein, n=3～15; The dibasic alcohol is polyethylene glycol, polytetrahydrofuran diol or polycaprolactone diol; The molar ratio of the modified rosin, dibasic alcohol and crosslinking agent is 1:1 ~1.5:0.5~1; the degradability of the rosin polyether ester elastomer is 12%~45%. 2. rosin polyether ester elastomer according to claim 1, is characterized in that, described linking agent is citric acid or glycerin. 3. a preparation method of the rosin polyether ester elastomer claimed in claim 1, is characterized in that, comprises: A) prepare the modified rosin shown in formula I; b) Mix modified rosin, glycol, and crosslinking agent in a molar ratio of 1:1 to 1.5:0.5 to 1 to obtain a mixture; the glycol is polyethylene glycol, polytetrahydrofuran glycol or polyethylene glycol Lactone diol; The modified rosin is a compound shown in formula I; c) heating the mixture, the modified rosin and the dibasic alcohol undergo ester condensation and are crosslinked by a crosslinking agent to obtain a rosin polyether ester elastomer; the degradability of the rosin polyether ester elastomer is 12 %~45%. 4. preparation method according to claim 3 is characterized in that, described linking agent is citric acid or glycerin. 5. The preparation method according to claim 3, characterized in that a first catalyst is added into the mixture, and the first catalyst accounts for 0.5%-1% by weight of the modified rosin. 6. The preparation method according to claim 5, wherein the first catalyst is zinc oxide, stannous oxalate or tetrabutyl titanate. 7. The preparation method according to claim 3, characterized in that step a) is specifically: a1) Mix rosin and polyether acrylate in a molar ratio of 1:0.5, add a second catalyst accounting for 0.5-1% of the mass of rosin to obtain a mixture; the structural formula of the polyether acrylate is:

Among them, n=3～15; a2) heating the mixture obtained in step a1), a Diels-Alder addition reaction occurs to obtain an addition product; a3) mixing the addition product with petroleum ether to separate out the modified rosin. 8. The preparation method according to claim 7, wherein the second catalyst is p-toluenesulfonic acid, hydroquinone or pyrocatechol. 9. preparation method according to claim 7, is characterized in that, described rosin is one or more of the abietic acid shown in formula II, III, IV or V:

10. The preparation method according to claim 7, characterized in that, the heating temperature in the step a2) is 170°C-220°C.

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